High purity perfluoroelastomer composites and a processes to produce the same

ABSTRACT

High purity perfluoroelastomer composites and processes for producing the same are provided. High purity composites may be formed from compositions comprising a crosslinkable fluoroelastomer terpolymer of TFE, PAVE, and CNVE, and functionalized PTFE, which may be crosslinked to form crosslinked composites having low metal content and low compression set. Emulsion mixtures for forming the high purity composites are also provided.

BACKGROUND OF THE INVENTION

Perfluoroelastomers have achieved outstanding commercial success and areused in a wide variety of applications in which severe environments areencountered, in particular those end uses where exposure to hightemperatures and aggressive chemicals occurs. For example, thesepolymers are often used in seals for aircraft engines, in semiconductormanufacturing equipment, in oil-well drilling devices, and in sealingelements for industrial equipment used at high temperatures.

The outstanding properties of perfluoroelastomers are largelyattributable to the stability and inertness of the copolymerizedperfluorinated monomer units that make up the major portion of thepolymer backbones in these compositions. Such monomers includetetrafluoroethylene (TFE) and perfluoro(alkyl vinyl) ethers (PAVE). Inorder to develop elastomeric properties fully, perfluoroelastomers aretypically crosslinked, i.e. vulcanized. To this end, a small percentageof cure site monomer is copolymerized with the perfluorinated monomerunits. Cure site monomers containing at least one nitrile group, forexample perfluoro-8-cyano-5-methyl-3,6-dioxa-1-octene, are especiallypreferred. Such compositions are described, for example, in U.S. Pat.Nos. 4,281,092; 4,394,489; 5,789,489; and 5,789,509.

The polymerization processes of perfluoroelastomers are most typicallydone in the presence of a perfluoro carboxylic acid salt or fluorinatedsulfonic acid salt. If the salt contains a metal ion, it contaminatesthe formed polymer. If the salt is a non-metal, usually the resulting pHof the polymerization media is acidic leading to corrosion ofpolymerization vessel or downstream lines and vessels, and subsequentcontamination of the resulting polymer. Further, coagulation of theemulsion or dispersion is usually accomplished by use of magnesium,barium, or other metallic salts resulting in two distinct problems.First, they add metallic contamination to the elastomeric crumb andsecond, the metallic salts of the perfluoro carboxylic acids become muchmore difficult to remove from the crumb.

The prior art further teaches compounding the perfluorelastomer, forexample, on a roll mill, Banbury mixer, extruder, or the like. In thisstep, crosslinking catalysts or other additives may be mixed with theperfluoroelastomer crumb in the melt to facilitate sufficientcrosslinking as may be required by the application. For example, onegoal may be to attain sufficient crosslinking to achieve good hightemperature compression set resistance. Compounding may actually resultin the addition of metallic and/or other contaminants by the directaddition via additives; additionally high temperature melt compoundingoften results in metal contamination by corrosion of the compoundingequipment and exposure to environmental contamination. If organiccrosslinking agents are used, the resulting articles are usually browndue to thermal decomposition of the agents.

Perfluoroelastomer articles such as seals, O-rings, and valve packingsare often highly filled with carbon black or metallic fillers forreinforcement rendering them opaque and providing an additional sourceof contamination. When exposed to plasmas in end uses such assemiconductor manufacturing, the polymeric component of these articlesis etched away, leaving the fillers as undesirable particlecontaminants. Furthermore, as the polymer decomposes any fillers such asmetals, metal oxides or metal salts originally contained in articles maybe released.

Recent patents of Saito et al. and Coughlin and Wang (U.S. Pat. No.5,565,512, and WO 02/48200) have discussed the value of producing clearand pure perfluoroelastomer parts with low metal ion contamination.Market forces that are driving the move to clear, cleanperfluoroelastomer parts include both the semi conductor industry andthe pharmaceutical industry which desires extremely low concentrationsof metals. In addition, the pharmaceutical and biotechnology industriesdesire overall purity and elimination of certain perfluoro carboxylicacids which accumulate in the body is highly desirable. For example,some companies manufacturing fluoropolymer resins or parts haveestablished limits of perfluoro octanoic acid (PFOA), the acid form ofammonium perfluoro octanoate (APFO) which is a common surfactant used influoromonomer emulsion polymerization.

However, the need for crosslinkable perfluoroelastomers and crosslinkedparts that have a low metallic ion contamination and a low perfluorocarboxylic concentration has not been met with the usual processes offorming these. Therefore, one embodiment of the present invention is amethod for producing perfluoroelastomer compositions having low metallicion contamination and low perfluoro carboxylic concentration.

SUMMARY OF THE INVENTION

This invention relates to crosslinkable perfluoroelastomers and curedperfluoroelastomer articles having low metallic ion concentration and alow concentration of residual fluorosurfactant, and inventive processesfor making the same. In the absence of additives, transparent articleshaving high purity are produced by the methods of the present invention.

In one embodiment, methods of the present invention minimizecontamination in part by minimizing corrosion that results fromconventional polymerization processes performed in the presence ofperfluorocarboxylic acid salt by using a non-metallic buffer and/orcorrosion resistant vessel and/or lines. Corrosion resistant materialsuseful in the present invention include high Ni alloys, for example,Inconel® or Hastelloy® alloys. Processes of present invention may alsosolve the problem of contamination encountered by coagulation of theemulsion or dispersion using metallic salts. For example, by usingnitric acid (HNO₃) or ammonium salts like (NH₄)₂CO₃ and NH₄NO₃ ascoagulants, metallic contamination can be minimized or eliminated. Knownmethods for curing elastomeric resin may result in contamination byusing compounding steps that add metallic and/or other contaminants, orby corrosion of the compounding equipment, or exposure to environmentalcontamination. It has been unexpectedly discovered thatperfluoroelastomeric uncrosslinked gum, having a low concentration ofperfluoro carboxylic acids or salt containing perfluoro cyano vinylether crosslink sites, such as 8-CNVE, can be cured in the mold at about250° C., or greater than 250° C., without a compounding step and withoutthe addition of any other chemicals.

Combining these inventive steps results in the production of crosslinkedperfluoro elastomer parts having metallic ion contamination more than afactor of 100 or a factor of 1000 lower than currently known. Forexample, in one embodiment of the present invention crosslinkedperfluoroelastomeric parts are produced having less than about 3 partsper million (ppm) or more preferably, less than about 0.5 ppm metallicion. The concentration of perfluoro carboxylic acid also may be lessthan about 2 ppm, or less than about 1 ppm. Advantageously, crosslinkedparts of the present invention may have compression set values measuringless than or equal to about 35% at about 200° C. Preferred crosslinkedparts are transparent and colorless.

DESCRIPTION OF THE FIGURES

FIG. 1. Curing kinetics of samples according to Example 2 obtained at250° C.

FIG. 2. Curing kinetics of samples according to Example 4 obtained at250° C.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the present invention is directed to a compositioncomprising a crosslinkable perfluoroelastomer terpolymer consistingessentially of TFE, PAVE and a cure site monomer having at least onenitrile-containing group; thus, the crosslinkable composition forms acrosslinked terpolymer without additional materials such as crosslinkingagents and the like. The present invention is further directed tomethods of making the crosslinkable terpolymer, methods of crosslinkingthe terpolymer in the absence of a crosslinking agent, and articles madetherefrom.

In one embodiment, perfluoroelastomers of the present invention maycomprise crosslinkable terpolymers polymerized from monomer unitsconsisting essentially of TFE, PAVE, and perfluorocyano vinyl ether. Inone embodiment the PAVE monomer is perfluoromethylvinyl ether (PMVE),however, other suitable perfluorinated vinyl ethers may also be selectedfrom monomers, or mixtures of monomers, of the formulaCF₂═CFO(Rf′O)_(n)(Rf″O)_(m)Rf   (I)where Rf′ and Rf″ are different linear or branched perfluoroalkylenegroups of 2-6 carbon atoms, m and n are independently 0-10, and Rf is aperfluoroalkyl group of 1-6 carbon atoms.

Another class of perfluorovinyl ethers for use in the present inventionincludes compositions of the formulaCF₂═CFO(CF₂CFXO)_(n)Rf   (II)where X is F or CF₃, n is 0-5, and Rf is a perfluoroalkyl group of 1-6carbon atoms.

A further class of perfluorovinyl ethers includes those ethers wherein nis 0 or 1 and Rf contains 1-3 carbon atoms. Examples of suchperfluorinated ethers include PMVE, perfluoroethyl vinyl ether (PEVE)and perfluoropropyl vinyl ether (PPVE). Other useful monomers includecompounds of the formulaCF₂═CFO[(CF₂)_(m)CF₂CFZO]_(n)Rf   (III)where Rf is a perfluoroalkyl group having 1-6 carbon atoms, m=0 or 1,n=0-5, and Z=F or CF₃. Preferred members of this class are those inwhich Rf is C₃F₇, m=0, and n=1.

Additional perfluorovinyl ether monomers for use in the presentinvention may include compounds of the formulaCF₂═CFO[(CF₂CFCF₃O)_(n)(CF₂CF₂CF₂O)_(m)(CF₂)_(p)]C_(x)F_(2x+1)   (IV)where m and n independently =1-10, p=0-3, and x=1-5. Preferred membersof this class include compounds where n=0-1, m=0-1, and x=1.

Another example of a useful perfluorovinyl ether includesCF₂═CFOCF₂CF(CF₃)O(CF₂O)_(m)C_(n)F_(2n+1)   (V)where n=1-5, m=1-3, and where, preferably, n=1.

Crosslinkable terpolymers of the present invention have cure sitemonomers containing at least one nitrile group. In one embodiment, themonomers include fluorinated olefins containing at least one nitrilegroup, and in another embodiment, the monomers comprisenitrile-containing fluorinated vinyl ethers, including those having thefollowing formulae.CF₂═CF—O(CF₂)₂—CN   (VI)where n=2-12, preferably 2-6;CF₂═CF—O[CF₂—CFCF₃—O]_(n)—CF₂—CF(CF₃)—CN   (VII)where n=04, preferably 0-2;CF₂═CF—[OCF₂CF(CF₃)]_(x)—O—(CF₂)_(n)—CN   (VIII)where x=1-2, and n=1-4; andCF₂═CF—O—(CF₂)_(n)—O—CF(CF₃)CN   (IX)where n=2-4. Particularly preferred cure site monomers areperfluorinated polyethers having a nitrile group and a trifluorovinylether group, including perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene),CF₂═CFOCF₂CF(CF₃OCF₂CF₂CN   (X).

Preferred perfluoroelastomer compositions of the present invention arecomprised of a crosslinkable terpolymer consisting essentially of unitsof TFE, PAVE and cure site units having at least one nitrile-containinggroup, where in one embodiment PAVE is PMVE and further, wherein8-perfluorocyano vinyl ether (8-CNVE) is the nitrile-containing curesite monomer. The crosslinkable terpolymer may be polymerized from theabove monomers by known methods including those described in WO02/060968 to Coggio et al. which is hereby incorporated by referenceherein, and further, methods as described in detail in the examplespresented below. In one embodiment, crosslinkable perfluoroelastomerterpolymers consist essentially of approximately from 38 to 81.7 molepercent TFE, 18 to 58 mole percent PAVE, and 0.3 to 4 mole percent of anitrile-containing cure site monomer. Other crosslinkable terpolymers ofthe present invention consist essentially of about 47 to 80 mole percentTFE, 19 to 50 mole percent PAVE, and 1 to 3 mole percentnitrile-containing cure site monomer.

After polymerization to form crosslinkable terpolymers of the presentinvention, the gum may be further processed with a finishing step asdescribed in Example 1 below which may facilitate the elimination ofsome contaminants.

In one embodiment, the highly pure crosslinkable terpolymers have lowmetal ion content (or metal contamination), as well as lowfluorosurfactant concentration. The metal content of the crosslinkableterpolymer is less than 200 ppm, and preferably less than 3000 parts perbillion (ppb), also preferred less than about 2000 ppb, furtherpreferred less than about 1000 ppb, more preferably less than about 500,and most preferably less than about 200 ppb when measured according tothe methods described herein for determining metal content. The metalcontent of preferred crosslinked terpolymer is also less than 200 ppm,preferably less than 3000 ppb, more preferably less than about 2000 ppb,further preferred less than about 1000 ppb or less than about 500 ppbwhen measured according to the methods described herein for determiningmetal content. In one embodiment, the fluorosurfactant concentration ispreferably less than 2 ppm for one or both of the uncrosslinked andcrosslinked terpolymer, when measured according to the methods describedherein. Preferably, the concentration of perfluoro carboxylic acid maybe less than about 2 ppm, and less than 1 ppm. Uncrosslinked andcrosslinked terpolymers may have a fluoro sulfonic acid concentration ofless than about 2 ppm, or less than 1 ppm. APFO concentrations ofuncrosslinked and crosslinked compositions may be less than 2 ppm or ina further embodiment less than 1 ppm.

The present invention is further directed to a process for making highlypure crosslinked perfluoroelastomeric articles. One embodiment of thepresent invention comprises a method comprising heating a compositioncomprising a crosslinkable terpolymer consisting essentially of TFE,PAVE, and nitrile-containing cure-site monomer units, to form highlypure crosslinked composition to which no crosslinking agents have beenadded. One method comprises:

1) forming a composition comprising a crosslinkable perfluoroelastomericterpolymer of the present invention consisting essentially of a) TFE, b)PAVE, and c) nitrile-containing cure site monomer;

2) shaping the crosslinkable perfluoroelastomeric terpolymercomposition;

3) heating said shaped perfluoroelastomeric terpolymer composition, and

4) crosslinking the perfluoroelastomer terpolymer by heating, whereinthe process is performed without adding or, in the absence of, acrosslinking agent.

The method of the present invention may include shaping by molding orother fabrication techniques by means that do not introduce significantmetallic contamination.

In one embodiment, the method comprises heating and crosslinking theterpolymer having units with nitrile-containing cure sites in theabsence of, or without the addition of, one or more crosslinking agents,until sufficient crosslinking is achieved. Crosslinking agents includingcoagents, catalysts, and the like (such as peroxides, isocyanurates,ammonia-generating compounds, and bisamidoxime) that are typically usedfor curing crosslinkable polymers, impart contaminants, and are notnecessary for crosslinking terpolymers using the novel methods of thepresent invention. The exclusion of these crosslinking agents from themethod of the present invention results in crosslinked compositionshaving higher purity than achieved by currently known methods. Preferredcrosslinked perfluoroelastomers are translucent or transparent afterheating.

In one embodiment, the method comprises heating and crosslinking shapedperfluoroelastomer to greater than or equal to about 250° C. in theabsence, or without the addition of crosslinking agents or additives,until sufficient crosslinking is achieved; in a further embodiment, themethod comprises heating to greater than or equal to about 300° C., inthe absence of, or without the addition of, crosslinking agents. Heatingand crosslinking are maintained at temperatures and for times sufficientto cure the terpolymer to a desired level. In a further embodiment, theheating and crosslinking are continued for times and temperaturesnecessary to obtain a specific compression set. For example, the methodcomprises heating and crosslinking until a crosslinked terpolymer orshaped article is formed having a compression set of less than or equalto about 50% when tested at about 200° C. according to the methoddescribed herein. In other embodiments the method comprises heating andcrosslinking until a crosslinked terpolymer or shaped article has acompression set of less than or equal to about 40%, less than or equalto about 35%, less than or equal to about 30%, or less than or equal toabout 10% when tested at about 200° C. according to the method usedherein, and described below. A crosslinkable terpolymer composition maybe heated, for example, for about 30 minutes or greater, or for about 60minutes or greater, at a temperature of greater than about 250° C. orgreater than or equal to about 300° C., to achieve these properties.Preferred crosslinked compositions of the present invention have acompression set less than or equal to about 40%, and more preferablyless than or equal to about 35%, when tested at about 200° C. accordingto the method described herein.

For use in evaluating the crosslinked compositions, compression set ismeasured according to ASTM D 395-01 Method B, at approximately 25%deflection, for about 70 hours in air. Articles are taken off from thetesting device and reheated to the testing temperature for one (1) hourand measured.

Articles made from the perfluoroelastomer terpolymer of the presentinvention are useful in applications requiring higher purity than can beobtained by currently known methods. A few uses of articles formed fromcompositions of the present invention include gaskets such as o-rings,tubes, diaphragms, seals and the like. Crosslinkable terpolymers of thepresent invention may be shaped and cured directly into usable articles.

In a further embodiment of the present invention the crosslinkableterpolymers may be blended with other materials, such as an additive orfiller, to impart or enhance desired properties, or, further, othermonomer or polymer compositions. Thus, in one embodiment a blend isformed comprising a composition comprising a crosslinkablefluoroelastomer terpolymer consisting essentially of TFE, PAVE and CNVE,and from about 1-20 wt %, based on the composite weight of at least oneadditional material selected from fillers and additives, which may beadded prior to shaping or forming the composite into an article. Forexample, one such composite of the present invention is formed having afiller comprising SiO₂, and preferably, where PAVE comprises PMVE, PEVE,or PPVE and CNVE comprises 8-CNVE. Crosslinkable fluoroelastomerterpolymer composites may have a metal content of less than about 3000ppb, less than about 2000 ppb, less than 1000 ppb, less than 500 ppb, orless than 200 ppb. Preferred composites, when crosslinked, have acompression set of less than 50%, less than 40% or less than 30%, whentested at 200° C.

In one other embodiment of the present invention, composites are formedfrom a blend comprising 1) a composition comprising a crosslinkableterpolymer consisting essentially of TFE, PAVE, and nitrile-containingcure site monomer units, such as the terpolymers of the presentinvention described above, and 2) functionalized polytetrafluoroethylene(PTFE). At least one additional material selected from fillers andadditives may be added. Composites of functionalized PTFE andcrosslinkable fluoroelastomer terpolymers also may have a metal contentof less than about 3000 ppb, less than about 2000 ppb, less than 1000ppb, less than 500 ppb, or less than 200 ppb. Preferred composites, whencrosslinked, have a compression set of less than 50%, less than 40% orless than 30%, when tested at 150° C.

The blends may be formed from an emulsion mixture of the crosslinkableterpolymers. In one embodiment, an emulsion mixture comprises anemulsion of a composition comprising a crosslinkable perfluoroelastomerterpolymer consisting essentially of units of TFE, PAVE, andperfluorocyano vinyl ether (CNVE), and a dispersion of at least oneadditional material selected from fillers and additives. In oneembodiment the emulsion of the composition comprising the terpolymer isa microemulsion, and the at least one additional material comprises adispersion of silica. Preferred terpolymers comprise units of PMVE,PPVE, or PEVE, and 8-CNVE. Methods for forming the emulsions are taught,for example, in the detailed examples herein.

In one other embodiment, an emulsion mixture comprises an emulsion of i)an emulsion comprising the crosslinkable perfluoroelastomer terpolymersof the present invention consisting essentially of units of TFE, PAVE,and CNVE, and ii) a PTFE polymer comprising 0.1-3 mol % perfluorocyanovinyl ether. Preferred terpolymers comprise units of PMVE, PPVE, orPEVE, and 8-CNVE. Methods for forming the emulsions are taught, forexample, in the detailed examples herein. Microemulsions andnanoemulsions of functionalized PTFE having particle sizes of less thanabout 100 nm are preferred. A nano emulsion comprising PTFE polymerfunctionalized with perfluorocyano vinyl ether, most preferably 8-cyanovinyl ether, and having a particle size of from about 10 nm to 100 nm ispreferred.

The emulsion mixtures of the present invention may be coagulated to formthe blends. For example, one blend of the present invention comprisingfunctionalized PTFE and crosslinkable perfluoroelastomer terpolymer iscoagulated to form a functionalized PTFE-filled crosslinkableperfluoroelastomer terpolymer blend, as described herein. Thefunctionalized PTFE may be present in an amount of about 1 to 20 wt % ofa dried composite resulting from the emulsion mixture, and thecrosslinkable perfluoroelastomer terpolymer in an amount of about 80-99wt % of a dried composite resulting from the emulsion mixture. Thefunctionalized PTFE-filled crosslinkable terpolymer blend may becrosslinked according to the methods described herein, including heatingand crosslinking the blend in the absence of any crosslinking agent, toform a cured functionalized PTFE-filled polymer having properties suchas a desired level of crosslinking, compression set and purity values asdescribed previously herein.

The blends may further comprise at least one additional material such asfillers and additives to impart specifically desired properties to thecomposite. The at least one additional material comprises about 1 to 20wt % of the composite, and in one embodiment it is added as a dispersionto an emulsion mixture. In one embodiment silica is added as adispersion to the microemulsions or the emulsion mixture. In oneembodiment, it is desired to add at least one additional material to afunctionalized PTFE-filled terpolymer blend prior to shaping, heatingand crosslinking the article.

Articles made from the functionalized PTFE-filled terpolymer include,gaskets such as o-rings, and the like.

Test Methods

APFO Analysis

The methanolic HCl derivitization method is used to change the APFO formfrom the salt or carboxylic acid into its methylester derivative. Thisform is easily analyzed via Gas Chromatography (GC).

The APFO in about 1 g polymer is extracted and derivitized into 10 mlMethanolic HCl (Part #33050-U, Supelco) over two hours at 55° C. Thederivative mixture is then combined with 20 ml of half saturatedNaCl/aqueous solution (98+%, Sigma Aldrich) and 10 ml n-Hexane (99+%,Sigma Aldrich). The derivative is extracted into the Hexane layer, whichis then removed for GC analysis.

The GC analysis is performed splitless using a non-polar column and anElectron Capture Detector (Examples 2, 3 and 4) or Flame IonizationDetector (Examples 5, 6 and 7).

EXAMPLES Example 1

An aqueous emulsion containing 10 g 8-CNVE[CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN], 135 g deionized (DI) water and 5 g 20 wt% ammonium perfluorooctanoate (APFO) aqueous solution was prepared byusing an Omini Mixer Homogenizer (Omini International Co.) for 5minutes. This solution is designated as “stock solution A”.

Approximately 1500 g DI water, 300 g 20 wt % APFO aqueous solution and16 g 8-CNVE were charged into an oxygen-free 4-liter reactor. Then, 190g TFE and 300 g PMVE were added into the reactor. The reactor was thenheated to 70° C. under 2285 KPa and the polymerization reaction wasinitiated by feeding 202 g ammonium persulfate (APS) aqueous solution (2g APS dissolved in 200 g DI water) within 2 minutes. As the reactionpressure decreased to 1800 KPa, 105 g stock solution A with 120 g DIwater and 20 g TFE were charged into the reactor within 3 minutes. Then,150.5 g APS solution (0.5 g APS dissolved in 150 DI water) was fed intothe reactor within 1 minute. As the reaction pressure decreased to 1600KPa, 45 g stock solution A with 150 g DI water and 20 g TFE were chargedinto the reactor within 1 minute. Then, 150.5 g APS solution (0.5 g APSdissolved in 150 g DI water) was added into the reactor within 1 minute.The polymerization reaction was stopped after 221 minutes from theinitiation of the reaction under 518 KPa. The reactor was cooled and theresidual gas was purged. The emulsion latex containing 16.9 wt % solidswas obtained.

Finishing Process 1

Approximately 10 ml nitric acid (minimum 65%, semiconductor grade,Riedel-deHaen) was introduced into 200 ml of the emulsion latex(prepared substantially according to Example 1) in a polypropylene (PP)beaker with stirring at room temperature. The liquids were decanted andthen the precipitated solids were immersed in 200 ml methanol(semiconductor grade, Riedel-deHaen) at room temperature. After 24hours, the methanol was decanted and the polymer was washed with 200 mlmethanol (semiconductor grade, Riedel-deHaen). The polymer was dried at120° C. for 12 hours in a convection oven.

Finishing Process 2:

The procedure is the same as the above, but the nitric acid used was anACS reagent grade (70%, Aldrich) and the methanol used was a PRA grade(99.9%, Aldrich).

The 2 dried polymer samples were analyzed by Inductively CoupledPlasma-Mass Spectroscopy (ICP-MS) for 16 metal elements. Table 1 liststhe metal ion levels in the polymers.

Solid-state ¹⁹F NMR was carried out to characterize the composition ofthe polymer. This polymer sample contained 62.4 mol % TFE, 36.6 mol %PMVE and 1.0 mol % 8-CNVE.

Example 2

An aqueous solution containing 10 g 8-CNVE[CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN], 136 g DI water and 4 g of 20 wt % APFOaqueous solution was prepared by using an Omini Mixer Homogenizer for 5minutes. This solution is designated as “stock solution B”.

Approximately 1500 g DI water, 300 g 20 wt % APFO aqueous solution and16 g 8-CNVE were charged into an oxygen-free 4-liter reactor. Then, 190g TFE and 320 g PMVE were added into the reactor. The reactor was thenheated to 70° C. under 2347 KPa and the polymerization reaction wasinitiated by feeding 200.5 g APS aqueous solution (0.5 g APS dissolvedin 200 g DI water) within 1 minute. As the reaction pressure decreasedto 1900 KPa, 105 g stock solution B with 120 g DI water and 20 g TFEwere charged into the reactor within 2 minutes. As the reaction pressuredecreased to 1700 KPa, 45 g stock solution B with 150 g DI water and 20g TFE were charged into the reactor within 2 minutes. The polymerizationreaction was stopped after 367 minutes from the initiation of thereaction under 600 KPa. The reactor was cooled and the residual gas waspurged. The emulsion latex containing 18.2 wt % solids was obtained.

Approximately 400 ml of the emulsion latex was coagulated at roomtemperature with 20 ml nitric acid (70%, ACS reagent, Aldrich) in a PPbeaker. The liquids were decanted and then the precipitated material wasimmersed in 400 ml methanol (99.9%, PRA grade, Aldrich) for 24 hours atroom temperature. Then, the methanol was decanted and the material waswashed with 400 ml methanol (99.9%, PRA grade, Aldrich). The methanolwas decanted and the washed material was dried at 70° C. for 48 hours ina convection oven.

The APFO residual detected from the polymer was 0.3 ppm. Solid-state ¹⁹FNMR showed it had 61.7 mol % TFE, 37.3 mol % PMVE and 1.0 mol % 8-CNVE.

An ARES rheometer (Rheometrics) was used to monitor the curing process.Disks having an 8 mm diameter and about a 0.8 mm thickness were moldedfrom the polymer at 100° C. for 2 minutes. A disk was placed between two8 mm diameter parallel plates at 60° C. for 100 seconds and then heatedto a setting curing temperature from a starting temperature of 60° C. ata heating rate of 80° C./min. Curing was carried out at a frequency of10 rad/second, a strain of 0.1% and a setting temperature in air. Torqueand Tan δ=G″/G′ were monitored with time, where G′ is the storage shearmodulus and G″ the loss shear modulus. Its curing curve is shown in FIG.1.

The crumb polymer was molded into AS-568A K214 (Aerospace StandardO-ring size) O-rings at 300° C. and 1727 psi for 1 hour and then werepostcured in air at 300° C. for 24 hours. The O-rings made weretransparent.

Compression set was measured on O-rings largely based on ASTM D 395-01Method B. However, the ASTM method does not have a quantitative time ortemperature scale as to how soon or at what temperature the testedspecimens should be taken off from the testing device. Differentcompression set values can be obtained when tested specimens are takenoff from the testing device at different temperatures. To avoid thisissue, tested specimens taken off from the testing device were reheatedto the testing temperature for 1 hour, and then measured according toASTM D 395-01, i.e., cooling for 30 minutes, etc. The compression setvalue is given in Table 3.

Example 3

An aqueous solution containing 10 g 8-CNVE[CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN], 480 g DI water and 10 g 20 wt % APFOaqueous solution was prepared by using an Omini Mixer Homogenizer for 5minutes. This solution is designated as “stock solution C”.

Approximately 1500 g DI water, 300 g 20 wt % APFO aqueous solution and16 g 8-CNVE were charged into an oxygen-free 4-liter reactor. Then, 260g TFE and 300 g PMVE were added into the reactor. The reactor was thenheated to 70° C. under 2584 KPa and the polymerization reaction wasinitiated by feeding 200.2 g APS aqueous solution (0.2 g APS dissolvedin 200 g DI water) within 1 minute. Then, stock solution C was fed intothe reactor as follows: Time after reaction initiation Stock solution Cadded (in minutes) (in grams) 2 60 16 60 28 60 40 60 51 50 61 60 72 6083 80 98 10

As the reaction pressure decreased to 2120 KPa, 20 g TFE was chargedinto the reactor within 1 minute. Another 20 g TFE was added into thereactor within 1 minute as the reaction pressure decreased to 1920 KPa.The polymerization reaction was stopped after 219 minutes from theinitiation of the reaction under 1200 KPa. The reactor was cooled andthe residual gas was purged. The emulsion latex containing 15.9 wt %solids was obtained.

The coagulation process was substantially the same as the firstfinishing process as shown in Example 1. The polymer was dried at 70° C.for 48 hours in a convection oven.

The dried polymer sample was analyzed by ICP-MS for 16 metal elements.Table 1 lists the metal ion levels in the polymer.

The APFO residual detected from the polymer was 1.2 ppm. This polymerhad 74.9 mol % TFE, 24.2 mol % PMVE and 0.9 mol % 8-CNVE, as determinedby solid-state ¹⁹F NMR.

The crumb polymer was molded into AS-568A K214 O-rings, heating at 300°C. and 1658 psi for 5 minutes, and then was postcured in air at 250° C.for 24 hours. The O-rings made were transparent. The compression setvalue is given in Table 3. The crumb polymer was also molded and curedinto 1 mm thick films between Kapton® films under the same molding,heating and postcuring condition. The purity of the crosslinked film isshown in Table 1.

Example 4

Approximately 1800 g DI water and 180 g 20 wt % APFO aqueous solutionwere charged into an oxygen-free 4-liter reactor. Then, 3.6 g 8-CNVE[CF₂═CF—O—(CF₂)₅—CN], 76 g PMVE and 62.8 g TFE were added into thereactor.

The reactor was heated to 60° C., and then the mixture of TFE with PMVE(55/45, wt/wt) was charged into the reactor until the pressure increasedto 920 KPa. Then 200 ml aqueous solution containing 6 g APS and 4 g 25wt % ammonium sulfite was added into the reactor to initiate thepolymerization reaction.

Once the initiation reaction started, 8-CNVE was continuously chargedinto the reactor at a rate of 0.143 g/min, and the mixture of TFE withPMVE (55/45 wt/wt) was also continuously supplied to the reactor tomaintain the reaction pressure at 930-950 KPa.

After 440 minutes from the start of the reaction initiation, the supplyof 8-CNVE and the mixture of TFE with PMVE was then stopped. The reactorwas kept in that state for another hour. Then reactor was cooled and theresidual gas was purged. The emulsion latex containing 27.5 wt % solidswas obtained.

The coagulation process is the same as the first finishing process asshown in Example 1. The polymer was dried at 70° C. for 48 hours in aconvection oven.

The dried polymer sample was analyzed by ICP-MS for 16 metal elements.Table 1 lists the metal ion levels in the polymer.

The APFO residual detected from the polymer was 0.8 ppm. Solid-state ¹⁹FNMR was carried out to characterize the composition of the polymer. Thispolymer sample contained 69.6 mol % TFE, 29.2 mol % PMVE and 1.2 mol %8-CNVE.

An ARES rheometer (Rheometrics) was used to monitor the curing process.Disks having an 8 mm diameter and about a 0.8 mm thickness were moldedfrom the polymer at 100° C. for 2 minutes. A disk was placed between two8 mm diameter parallel plates. Curing was carried out at a frequency of10 rad/second, a strain of 0.5% and heating at about 250° C. in air.Torque and Tan δ=G″/G′ were monitored with time. Its curing curve isshown in FIG. 2.

The crumb polymer was molded into AS-568A K214 O-rings heating at 250°C. and 1727 psi for 30 min and then was postcured in air at 90° C. for 4hours, 204° C. for 24 hours and 288° C. for 24 hours. The O-rings madewere transparent. The compression set value is given in Table 3. Thecrumb polymer was also molded into 1 mm think films between Kapton®films under the same molding and postcuring condition. The purity of thecrosslinked film is shown in Table 1.

Example 5

An aqueous solution containing 5 g 8-CNVE[CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN], 490 g DI water and 10 g 20 wt % APFOaqueous solution was prepared by using an Omini Mixer Homogenizer for 5minutes. This solution is designated as “stock solution E”.

Approximately 1500 g DI water, 300 g 20 wt % APFO aqueous solution and 8g 8-CNVE were charged into an oxygen-free 4-liter reactor. Then, 190 gTFE and 300 g PMVE were added into the reactor. The reactor was thenheated to 70° C. under 2258 KPa and the polymerization reaction wasinitiated by feeding 200.5 g APS aqueous solution (0.5 g APS dissolvedin 200 g DI water) within 1 minute. Then, stock solution E was fed intothe reactor as follows: Time after reaction initiation Stock solution Eadded (in minutes) (in grams) 3 100 12 115 23 65 29 90 38 80 43 50

As the reaction pressure decreased to 1800 KPa, 20 g TFE was chargedinto the reactor within 1 minute. Another 20 g TFE was added into thereactor within 1 minute as the reaction pressure decreased to 1600 KPa.The polymerization reaction was stopped after 198 minutes from theinitiation of the reaction under 600 KPa. The reactor was cooled and theresidual gas was purged. The emulsion latex collected containing 17.3 wt% solids was obtained. The polymer had 49.6 wt % TFE, 48.5 wt % PMVE and1.9 wt % 8-CNVE determined by FTIR.

Fumed silica (1.73 g) (R812, Degussa) was dispersed in 50 ml 2-propanol(IPA) (99.8%, PR grade, Aldrich). This fumed silica IPA dispersion wasthen introduced into 100 g of the polymer emulsion with stirring at roomtemperature. This mixture was coagulated with 5 ml nitric acid (70%, ACSreagent, Aldrich). The liquids were decanted and then the precipitatedmaterial was immersed in 100 ml methanol (99.9%, PRA grade, Aldrich) for24 hours at room temperature. Then, the methanol was decanted and thematerial was washed with 100 ml methanol. The methanol was decanted andthe washed material was dried at 70° C. for 48 hours in a convectionoven.

The dried polymer sample was analyzed by ICP-MS for 16 metal elements.Table 2 lists the metal ion levels in the polymer. The APFO residualdetected in the dried silica-filled polymer was less than 2 ppm.

The silica-filled polymer was molded into AS-568A K214 O-rings heatingat 250° C. and 1727 psi for 30 minutes and then was post cured in air at250° C. for 24 hours. The compression set value is given in Table 3.

Example 6

Preparation of TFE-PMVE-8CNVE Terpolymer Emulsion:

An aqueous solution containing 20 g 8-CNVE[CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN], 490 g DI water and 11 g 20 wt % APFOaqueous solution was prepared by using an Omini Mixer Homogenizer for 5minutes. This solution is designated as “stock solution F”.

Approximately 1500 g DI water, 300 g 20 wt % APFO aqueous solution and32 g 8-CNVE were charged into an oxygen-free 4-liter reactor. Then, 190g TFE and 300 g PMVE were added into the reactor. The reactor was thenheated to 70° C. under 2250 KPa and the polymerization reaction wasinitiated by feeding 200.5 g APS aqueous solution (0.5 g APS dissolvedin 200 g DI water) within 2 minutes. Then, stock solution F was fed intothe reactor as follows: Time after reaction initiation Stock solution Fadded (in minutes) (in grams) 2 70 14 70 26 70 39 45 53 50 102 105 12890

As the reaction pressure decreased to 1800 KPa, 20 g TFE was chargedinto the reactor within 1 minute. Another 20 g TFE was added into thereactor within 1 minute as the reaction pressure decreased to 1600 KPa.The polymerization reaction was stopped after 465 minutes from theinitiation of the reaction under 730 KPa. The reactor was cooled and theresidual gas was purged. The emulsion latex containing 17.4 wt % solidswas obtained. The polymer had 58.7 mol % TFE, 38.2 mol % PMVE and 3.1mol % 8CNVE, as determined by solid-state ¹⁹F NMR.

Preparation of 8-CNVE Functionalized Nano PTFE Emulsion:

Approximately 1700 g DI water, 300 g 20 wt % APFO aqueous solution, 45 ghexafluorobenzene (HFB) and 3.5 g 8-CNVE [CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN]were charged into an oxygen-free 4-liter reactor. Then, 130 g TFE wasadded into the reactor. The reactor was then heated to 70° C. under 1200KPa and the polymerization reaction was initiated by feeding 200.5 g APSaqueous solution (0.5 g APS dissolved in 200 g DI water) within 3minutes. About 820 g TFE was fed into the reactor to keep a constantpressure of 1200 KPa within 322 minutes. The reactor was cooled and theresidual gas was purged. A nano emulsion latex containing 24.2 wt %solids was obtained. The average size of PTFE particles was 19.4 nm indiameter measured by dynamic light scattering (90 Plus, BrookhavenInstruments). The polymer had 99.9 mol % TFE and 0.1 mol % 8-CNVE, asdetermined by solid-state ¹⁹F NMR.

Approximately 100 g of the terpolymer emulsion was mixed with 14.4 g ofthe nano PTFE emulsion. The emulsion mixture was coagulated with 5 mlnitric acid (70%, ACS reagent, Aldrich). The liquids were decanted andthen the precipitated material was immersed in 100 ml methanol (99.9%,PRA grade, Aldrich) for 24 hours at room temperature. Then, the methanolwas decanted and the material was washed with 100 ml methanol. Themethanol was decanted and the washed material was dried at 70° C. for 48hours in a convection oven forming a functionalized nano PTFE-filledpolymer composite. The APFO residual detected in the dried polymer wasless than 2 ppm.

The functionalized nano PTFE-filled polymer was molded into AS-568A K214O-rings heating at 300° C. and 1727 psi for 30 minutes and thenpostcured in air at 250° C. for 24 hours. The O-rings made weretransparent. The compression set value is given in Table 3.

Example 7

Preparation of 8-CNVE Functionalized Nano PTFE Emulsion:

Approximately 1700 g DI water, 300 g 20 wt % APFO aqueous solution, 45 gHFB and 7 g 8-CNVE [CF₂═CF—O—(CF₂)₃—O—CF(CF₃)—CN] were charged into anoxygen-free 4-liter reactor. Then, 120 g TFE was added into the reactor.The reactor was then heated to 70° C. under 12 bar and thepolymerization reaction was initiated by feeding 200.5 g APS aqueoussolution (0.5 g APS dissolved in 200 g DI water) within 3 minutes. 760 gTFE was fed into the reactor to keep a constant pressure of 12 barswithin 447 minutes. The reactor was cooled and the residual gas waspurged. The emulsion latex containing 26.8 wt % solids was obtained. Theaverage size of the PTFE particles was 24.3 nm in diameter determined bydynamic light scattering. The polymer had 99.8 mol % TFE and 0.2 mol %8-CNVE, as determined by solid-state ¹⁹F NMR.

Approximately 100 g of the terpolymer emulsion made in Example 6 wasmixed with 13 g of the nano PTFE emulsion. The emulsion mixture wascoagulated with 5 ml nitric acid (70%, ACS reagent, Aldrich). Theliquids were decanted and then the precipitated material was immersed in100 ml methanol (99.9%, PRA grade, Aldrich) for 24 hours at roomtemperature. Then, the methanol was decanted and the material was washedwith 100 ml methanol. The methanol was decanted and the washed materialwas dried at 70° C. for 48 hours in a convection oven.

The dried polymer sample was analyzed by ICP-MS for 16 metal elements.Table 2 lists the metal ion levels in the polymer. The APFO residualdetected in the resulting dried functionalized nano PTFE-filled polymerwas less than 2 ppm.

The functionalized nano PTFE-filled polymer was molded into AS-568A K214O-rings heating at 300° C. and 1727 psi for 30 minutes, and thenpostcured in air at 250° C. for 24 hours. The O-rings made weretransparent. The compression set value is given in Table 3. TABLE 1Metal ions detected in the crosslinkable polymers and the crosslinkedparts. Ex. 1⁽²⁾ Ex. 3⁽³⁾ Ex. 3⁽⁴⁾ Ex. 4⁽⁵⁾ Ex. 4⁽⁶⁾ Ex. 1⁽¹⁾ Level LevelLevel Level Level Level Detected Detected Detected Detected DetectedDetected Metal Ions (ppb) (ppb) (ppb) (ppb) (ppb) (ppb) Al 1 <1 <1 12 18 Ba <1 <1 1 1 <1 <1 Ca 37 15 50 100 20 70 Cr 6 <5 <5 <5 <5 13 Cu <5 <5<5 <5 <5 <5 Fe 17 10 <10 <10 <10 30 Pb <1 <1 <1 <1 <1 <1 Li 1 3 <1 <1 <1<1 Mg 1 1 18 29 12 23 Mn 1 1 2 3 <1 2 Ni 36 37 16 14 27 33 K 11 <10 <10<10 <10 10 Na 70 8 22 26 9 200 Sr <1 <1 <1 <1 <1 <1 Ti <10 <10 <10 <10<10 <10 Zn <10 <10 <10 <10 <10 <10⁽¹⁾The polymer obtained by finishing process 2.⁽²⁾The polymer obtained by finishing process 1.⁽³⁾The crumb polymer.⁽⁴⁾The crosslinked film.⁽⁵⁾The crumb polymer.⁽⁶⁾The crosslinked film.

TABLE 2 Metal ions detected in the crosslinkable polymer composites. Ex.5 Ex. 7 Metal Ions Level Detected (ppb) Level Detected (ppb) Al 8 4 Ba 43 Ca <10 20 Cr <5 <5 Cu 24 9 Fe 60 50 Pb <1 <1 Li <1 <1 Mg <1 3 Mn 1 2Ni 5 11 K <10 <10 Na <5 <5 Sr <1 <1 Ti <10 <10 Zn <10 <10

TABLE 3 Compression set values. Compression set, %* Example 2 65⁽¹⁾Example 3 35⁽¹⁾ Example 4  7⁽¹⁾ Example 5 31⁽²⁾ Example 6 33⁽³⁾ Example7 39⁽³⁾*25% deflection, 70 hours, in air;⁽¹⁾204° C.;⁽²⁾200° C.;⁽³⁾150° C.

1. An emulsion mixture comprising i) a microemulsion of a compositioncomprising a crosslinkable fluoroelastomer terpolymer consistingessentially of tetrafluoroethylene (TFE), perfluoroalkyl vinyl ether(PAVE), and perfluorocyano vinyl ether (CNVE) monomer units, and ii) amicroemulsion comprising a functionalized polytetrafluoroethylene (PTFE)polymer comprising 0.1 to 3 mol % perfluorocyano vinyl ether (CNVE),wherein the particle size of the functionalized PTFE polymer is about 10nm to 100 nm and wherein a composite comprising functionalizedPTFE-crosslinkable fluoroelastomer terpolymer isolated from thisemulsion mixture contains less than 3000 ppb of metals.
 2. The emulsionmixture of claim 1, wherein CNVE in the crosslinkable fluoroelastomerterpolymer, is 8-CNVE.
 3. The emulsion mixture of claim 1, wherein theCNVE in the functionalized PTFE polymer is 8-CNVE.
 4. The emulsionmixture of claim 1, wherein PAVE is perfluoromethyl vinyl ether (PMVE).5. The emulsion mixture of claim 1, wherein PAVE is perfluoropropylvinyl ether (PPVE).
 6. The emulsion mixture of claim 1, wherein PAVE isperfluoroethyl vinyl ether (PEVE).
 7. The emulsion mixture of claim 1,wherein the functionalized PTFE is about 1 to 20 wt % of a driedcomposite resulting from the emulsion mixture and the crosslinkablefluoroelastomer terpolymer is about 80 to 99 wt % of the dried compositeresulting from the emulsion mixture.
 8. The emulsion mixture of claim 1,further comprising at least one additional material selected fromfillers and additives.
 9. The emulsion mixture of claim 1, wherein atleast one filler or additive is in the form of a dispersion.
 10. Theemulsion mixture of claim 1, further comprising silica in the form of adispersion.
 11. (canceled)
 12. The emulsion mixture of claim 1, whereinthe crosslinkable fluoroelastomer composite has less than about 2000 ppbmetal content.
 13. The emulsion mixture of claim 1, wherein thecrosslinkable fluoroelastomer composite has less than about 1000 ppbmetal content.
 14. The emulsion mixture of claim 1, wherein thecrosslinkable fluoroelastomer composite has less than about 500 ppbmetal content.
 15. The emulsion mixture of claim 1, wherein thecrosslinkable fluoroelastomer composite has less than about 200 ppbmetal content.
 16. An emulsion mixture comprising i) a microemulsion ofa composition comprising a crosslinkable fluoroelastomer terpolymerconsisting essentially of tetrafluoroethylene (TFE), perfluoroalkylvinyl ether (PAVE), and perfluorocyano vinyl ether (CNVE) monomer units,and ii) a dispersion of at least one additional material selected fromfiller and additives.
 17. The emulsion of claim 16, wherein the at leastone additional material comprises a dispersion of silica.
 18. Theemulsion of claim 16, wherein CNVE is 8-CNVE.
 19. The emulsion mixtureof claim 16, wherein a crosslinkable fluoroelastomer composite formedfrom the emulsion mixture has less than about 3000 ppb metal content.20. The emulsion mixture of claim 16, wherein a crosslinkablefluoroelastomer composite formed from the emulsion mixture has less thanabout 2000 ppb metal content.
 21. The emulsion mixture of claim 16,wherein a crosslinkable fluoroelastomer composite formed from theemulsion mixture has less than about 1000 ppb metal content.
 22. Theemulsion mixture of claim 16, wherein a crosslinkable fluoroelastomercomposite formed from the emulsion mixture has less than about 500 ppbmetal content.
 23. The emulsion mixture of claim 16, wherein acrosslinkable fluoroelastomer composite formed from the emulsion mixturehas less than about 200 ppb metal content.
 24. A crosslinkable compositecomprising i) a composition comprising a crosslinkable fluoroelastomerterpolymer consisting essentially of tetrafluoroethylene (TFE),perfluoromethyl vinyl ether (PMVE) and perfluorocyano vinyl ether(CNVE), and ii) at least one additional material selected from fillersand additives, wherein the crosslinkable composite has less than about3000 ppb metal content, and wherein the composite when crosslinked has acompression set of less than 50% when tested at 200° C.
 25. Thecomposite of claim 24 wherein the composition further comprises SiO₂.26. The composite of claim 24, wherein the compression set is less thanabout 40%.
 27. The composite of claim 24 wherein the compression set isless than about 30%.
 28. The composite of claim 24 wherein thecompression set is less than about 20%.
 29. The composite of claim 24wherein the at least one additional material is about 1 to 20 wt % ofthe composite.
 30. The composite of claim 24 wherein the crosslinkablefluoroelastomer terpolymer comprises 8-CNVE.
 31. The composite of claim24 wherein the crosslinkable terpolymer has a metal content of less thanabout 2000 ppb.
 32. The composite of claim 24 wherein the crosslinkableterpolymer has a metal content of less than about 1000 ppb.
 33. Thecomposite of claim 24 wherein the crosslinkable terpolymer has a metalcontent of less than about 500 ppb.
 34. The composite of claim 24wherein the crosslinkable terpolymer has a metal content of less thanabout 200 ppb.
 35. (canceled)
 36. The composite of claim 24 wherein thecomposite has a metal content of less than about 2000 ppb.
 37. Thecomposite of claim 24 wherein the composite has a metal content of lessthan about 1000 ppb.
 38. The composite of claim 24 wherein the compositehas a metal content of less than about 500 ppb.
 39. The composite ofclaim 24 wherein the crosslinkable terpolymer has a metal content ofless than about 200 ppb.
 40. A crosslinkable composite comprising i) acomposition comprising a crosslinkable fluoroelastomer terpolymerconsisting essentially of tetrafluoroethylene (TFE), perfluoromethylvinyl ether (PMVE) and perfluorocyano vinyl ether (CNVE), and ii) acomposition comprising a functionalized polytetrafluoroethylene (PTFE)polymer comprising crosslinkable moieties having a particle size of 10nm to 100 nm wherein the crosslinkable composite has less than about3000 ppb metal content, and further, wherein when the PTFE and thefluoroelastomer terpolymer are crosslinked to form a crosslinkedcomposite, the crosslinked composite has a compression set of less than50% when tested at 150° C.
 41. The composite of claim 40 wherein thePTFE polymer is crosslinked with the crosslinkable fluoroelastomerterpolymer.
 42. The composite of claim 40 wherein the crosslinkablemoieties of the functionalized PTFE are perfluorocyano vinyl ether. 43.The composite of claim 40 wherein the crosslinkable moieties of thefunctionalized PTFE are 8-CNVE.
 44. The composite of claim 40 whereinthe crosslinkable fluoroelastomer terpolymer comprises 8-CNVE.
 45. Thecomposite of claim 40 wherein the composite further comprises at leastone additional material selected from fillers and additives.
 46. Thecomposite of claim 40 wherein the composite further comprises SiO₂. 47.The composite of claim 40 wherein the filler comprises about 1 to 20 wt% of the composite.
 48. (canceled)
 49. (canceled)
 50. (canceled) 51.(canceled)
 52. (canceled)
 53. The composite of claim 40 wherein thecomposite has a metal content of less than about 2000 ppb.
 54. Thecomposite of claim 40 wherein the composite has a metal content of lessthan about 1000 ppb.
 55. The composite of claim 40 wherein the compositehas a metal content of less than about 500 ppb.
 56. The composite ofclaim 40 wherein the composite has a metal content of less than about200 ppb.
 57. The emulsion mixture of claim 1 wherein the fluoroelastomercomposite has less than 2 ppm APFO.
 58. The composite of claim 24wherein the composite has an APFO concentration of less than 2 ppm. 59.The composite of claim 40 wherein the composite contains no more than2.0 ppm APFO.